Nano-assisted inclusion separation of alkali metals from basic solutions was reported by inclusion-facilitated emulsion liquid membrane process. The novelty of this study is the application of nano-baskets of calixcrown in the selective and efficient separation of alkali metals as both the carrier and the surfactant. For this aim, four derivatives of diacid calix[4]-1,2-crowns were synthesized, and their inclusion-extraction parameters were optimized including the calixcrown scaffold (13, 4 wt%) as the carrier/demulsifier, the commercial kerosene as diluent in membrane, sulphonic acid (0.2 M) and ammonium carbonate (0.4 M) as the strip and the feed phases, the phase and the treat ratios of 0.8 and 0.3, mixing speed (300 rpm), and initial solute concentration (100mg/L). The selectivity of membrane over more than ten interfering cations was examined and the results revealed that under the optimized operating condition, the degree of inclusion-extraction of alkali metals was as high as 98-99%.